Decarboxylative Allylation of Glyoxylic Acids with Diallyl Carbonate

A catalyst system consisting of Pd(PPh3)4 and P(pTol)3 was found to effectively promote the intermolecular decarboxylative coupling of α‐oxocarboxylic acids with diallyl carbonate to give α,β‐unsaturated ketones. The key advantage of the new reaction protocol is that preformation of the allyl esters...

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Bibliographic Details
Published in:European journal of organic chemistry 2012-09, Vol.2012 (25), p.4680-4683
Main Authors: Manjolinho, Filipe, Grünberg, Matthias F., Rodríguez, Nuria, Gooßen, Lukas J.
Format: Article
Language:English
Subjects:
Acids
Allylation
C-C bond formation
Catalysis
Catalysts: preparations and properties
Chemistry
Coordination compounds
Decarboxylation
Exact sciences and technology
General and physical chemistry
Inorganic chemistry and origins of life
Organocatalysis
Palladium
Preparations and properties
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary:A catalyst system consisting of Pd(PPh3)4 and P(pTol)3 was found to effectively promote the intermolecular decarboxylative coupling of α‐oxocarboxylic acids with diallyl carbonate to give α,β‐unsaturated ketones. The key advantage of the new reaction protocol is that preformation of the allyl esters is not required. The reaction is believed to proceed via phosphane‐mediated decarboxylation of the α‐oxocarboxylates, leading to acyl anion equivalents that are allylated within the coordination sphere of the palladium catalyst. Under the reaction conditions, the double bond then migrates into conjugation with the carbonyl group. An efficient and mild protocol for the intermolecular decarboxylative allylation ofarylglyoxylic acids with diallyl carbonate is described. Using P(pTol)3 as an organocatalyst, acyl anion equivalents are generated in situ from the corresponding arylglyoxylic acid, followed by palladium‐catalyzed allylation and isomerization to afford α,β‐unsaturated ketones in good to excellentyields.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201200766